JP2704670B2 - Photoreceptor for organic electrophotography - Google Patents
Photoreceptor for organic electrophotographyInfo
- Publication number
- JP2704670B2 JP2704670B2 JP33078190A JP33078190A JP2704670B2 JP 2704670 B2 JP2704670 B2 JP 2704670B2 JP 33078190 A JP33078190 A JP 33078190A JP 33078190 A JP33078190 A JP 33078190A JP 2704670 B2 JP2704670 B2 JP 2704670B2
- Authority
- JP
- Japan
- Prior art keywords
- photoreceptor
- protective layer
- organic
- layer
- charge transfer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 108091008695 photoreceptors Proteins 0.000 title claims description 18
- 239000010410 layer Substances 0.000 claims description 27
- 239000011241 protective layer Substances 0.000 claims description 27
- 238000012546 transfer Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000002609 Pyrus pyrifolia var. culta Species 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は有機電子写真用感光体、特に耐摩耗性にすぐ
れた有機電子写真用感光体に関するものである。Description: TECHNICAL FIELD The present invention relates to a photoconductor for organic electrophotography, and more particularly to a photoconductor for organic electrophotography having excellent abrasion resistance.
（従来技術） 有機化合物光導電層を用いた電子写真感光体として、
第１図のように導電性支持体（１）の面上に、フタロシ
アニン系材による電荷発生層（２）と、ブタジエン，ヒ
ドラジン系材による絶縁保護層を兼ねる電荷移動層
（３）を形成したものが多く使用されるようになりつつ
ある。(Prior art) As an electrophotographic photoreceptor using an organic compound photoconductive layer,
As shown in FIG. 1, a charge generation layer (2) made of a phthalocyanine-based material and a charge transfer layer (3) also serving as an insulating protective layer made of a butadiene- or hydrazine-based material were formed on the surface of a conductive support (1). Things are increasingly being used.
この感光体は電荷移動層（３）が電荷発生層（２）の
表面を厚く覆っているため、一般に感度低下に伴う黒す
じ、白すじ等は起きにくい。In this photoreceptor, since the charge transfer layer (3) covers the surface of the charge generation layer (2) thickly, black streaks, white streaks, and the like due to a decrease in sensitivity generally do not occur.
しかしその反面耐摩耗性に劣るため寿命が短く、しか
も繰り返し使用による膜厚の減少により、帯電性の劣化
を生ずる問題がある。However, on the other hand, there is a problem that the life is short due to poor abrasion resistance, and the chargeability is deteriorated due to a decrease in the film thickness due to repeated use.
そこで耐摩耗性を向上させるため、従来以下に述べる
材料および形成方法により、電荷移動層（３）の表面
に、第１図中に点線によって図示する透明絶縁保護層
（４）を設けることが提案されている。この方法は、ポ
リウレタン，ポリエステル，ポリカーボネートなどの高
分子材料を、一般溶剤であるトリクレンやクロロホルム
などにより溶解調合し、これをスプレー，リングコート
等で透明絶縁保護層を形成する方法である。また他の方
法はポリビニルホルマール樹脂、或いは変成ホルマール
樹脂を、トリクロルエチレン，モノクロールベンゼン，
クレゾール，キシロールまたはこれらの混合物中に溶解
させたものを、浸漬法やスプレー法などにより塗布し
て、透明絶縁保護層（４）を形成する方法である。Therefore, in order to improve the wear resistance, it has been proposed to provide a transparent insulating protective layer (4) shown by a dotted line in FIG. 1 on the surface of the charge transfer layer (3) using the materials and forming methods described below. Have been. In this method, a polymer material such as polyurethane, polyester, or polycarbonate is dissolved and mixed with a general solvent such as trichlene or chloroform, and this is formed by spraying, ring coating, or the like to form a transparent insulating protective layer. Another method is to use polyvinyl formal resin or modified formal resin by adding trichloroethylene, monochlorobenzene,
This is a method in which a transparent insulating protective layer (4) is formed by applying cresol, xylol or a solution thereof in a mixture thereof by dipping or spraying.
（従来技術の問題点） しかし有機光導電層にあっては、溶媒としてトリクレ
ンなどの一般溶媒を用いた場合には、透明保護層が形成
される電荷移動層（３）が溶媒により侵されて、保護層
（４）中に不純物の拡散をもたらす。従って保護層
（４）としての十分な強度が得られにくいため、耐摩耗
性の向上が十分でないばかりでなく、画像に不純物の影
響が現われて、鮮明かつ安定した画像が得られにくい大
きな欠点がある。(Problems of the prior art) However, in the case of using a general solvent such as trichlene as the solvent in the organic photoconductive layer, the charge transfer layer (3) on which the transparent protective layer is formed is attacked by the solvent. And diffusion of impurities into the protective layer (4). Therefore, it is difficult to obtain a sufficient strength as the protective layer (4), so that not only the abrasion resistance is not sufficiently improved, but also the effect of impurities on the image appears, and a clear and stable image is hardly obtained. is there.
（問題点を解決するための本発明の手段） 良好な画質の像を得ながら十分な耐摩耗性を実現する
ためには、従来方法のように電荷移動層そのものの特性
を変えることなく、電荷移動層以上の自己潤活性をもっ
た保護膜の形成が重要である。(Means of the Invention for Solving the Problems) In order to realize sufficient wear resistance while obtaining an image of good image quality, the charge transfer layer itself must be changed without changing the characteristics of the charge transfer layer itself as in the conventional method. It is important to form a protective film having a self-wetting activity higher than that of the transfer layer.
本発明者らは以上から種々検討を重ねた結果、酢酸ま
たはギ酸またはこれらの混合溶媒中に溶解させたポリビ
ニルホルマールによる絶縁保護層の形成が、耐摩耗性の
向上と画質の低下防止に大きな効果を発揮することを明
らかにしてなされたものである。As a result of various studies from the above, the present inventors have found that formation of an insulating protective layer of polyvinyl formal dissolved in acetic acid or formic acid or a mixed solvent thereof has a great effect on improving abrasion resistance and preventing deterioration of image quality. It is made clear that it exerts.
即ち本発明は第１図によって前記した導電性支持体
（１）上に電荷発生層（２）を形成し、更にその面上に
電荷移動層（３）を形成した有機電子写真用感光体にお
いて、第２図に示すように電荷移動層（３）の面上に、 によって示されるポリビニルホルマール絶縁保護層
（５）を設けたことを特徴とするものであって、このポ
リビニルホルマールは、特にアルコール基が４〜９％，
アセテート基が９〜13％、平均重合度が450以上のもの
が好ましい。また塗布後の乾燥は80〜120度の範囲内の
温度で行って硬化させることが好ましい。That is, the present invention relates to a photoreceptor for organic electrophotography wherein a charge generation layer (2) is formed on the conductive support (1) described above with reference to FIG. 1 and a charge transfer layer (3) is further formed on the surface. As shown in FIG. 2, on the surface of the charge transfer layer (3), Wherein a polyvinyl formal insulating protective layer (5) is provided, wherein the polyvinyl formal has an alcohol group of 4 to 9%,
Those having an acetate group of 9 to 13% and an average degree of polymerization of 450 or more are preferred. It is preferable that drying after application is performed at a temperature in the range of 80 to 120 ° C. for curing.
（作用） 本発明に用いられる保護層形成用の高分子材料の溶媒
として用いられる酢酸，ギ酸またはこれらの混合物など
の特定の溶媒は、ブタジエン，ヒドラゾン系材料による
電荷移動層を溶解してその特性を変化させるものではな
い。従って前記したような絶縁保護層（５）中への不純
物の拡散による保護層（５）の強度の低下を防ぐことが
できるので、従来方法に比べて耐摩耗性を大きく向上で
き、しかも画質の低下を防ぐことができる。次に本発明
の実施例を従来方法による比較例と対比して説明する。(Function) A specific solvent such as acetic acid, formic acid, or a mixture thereof used as a solvent of the polymer material for forming the protective layer used in the present invention dissolves the charge transfer layer made of a butadiene or hydrazone-based material and has a characteristic. It does not change. Therefore, it is possible to prevent the strength of the protective layer (5) from being reduced due to the diffusion of impurities into the insulating protective layer (5) as described above. Drop can be prevented. Next, an example of the present invention will be described in comparison with a comparative example using a conventional method.
（実施例１） アルミニウム支持体上に電荷発生層を設け、さらにこ
の上に電荷移動層を設けてなる有機電子写真用感光体の
電荷移動層面上に、酢酸300部中に完全溶解させたポリ
ビニルホルマール50部を塗布したのち、温度100℃で２
時間加熱して保護層を形成した。この保護層の厚さは２
μｍであり、鉛筆硬度法による硬度は5Hであった。また
この感光体を帯電，露光，現像，転写，およびクリーニ
ングからなる公知の電子写真装置に組込んで複写を行っ
たところ、本発明保護層を設けない感光体は６万枚の複
写で帯電劣化を生じてかぶりを発生するが、本発明絶縁
保護層を設けた感光体では12万枚の複写を行っても画像
の乱れがなかった。また絶縁保護層の感光体に対する接
着性を調べるため、セロハンテープによる剥離テストを
行ったところ、全く剥離部分を認めることができなかっ
た。Example 1 Polyvinyl completely dissolved in 300 parts of acetic acid was formed on a charge transfer layer of an organic electrophotographic photoreceptor having a charge generation layer provided on an aluminum support and further provided with a charge transfer layer thereon. After applying 50 parts of formal, 2
Heating was performed for a time to form a protective layer. The thickness of this protective layer is 2
μm and the hardness by the pencil hardness method was 5H. When this photoconductor was incorporated in a known electrophotographic apparatus including charging, exposure, development, transfer, and cleaning, and copying was performed, the photoconductor without the protective layer of the present invention was degraded by charging after 60,000 copies. However, the photoreceptor provided with the insulating protective layer of the present invention did not disturb the image even after copying 120,000 sheets. Further, a peeling test using a cellophane tape was performed to examine the adhesiveness of the insulating protective layer to the photoreceptor. As a result, no peeled portion could be recognized.
（実施例２） 実施例１と同じ有機電子写真用感光体の電荷移動層の
面上に、ギ酸100部中にポリビニルホルマール50部を完
全溶解させたものを塗布したのち、温度80℃で20時間加
熱して絶縁保護層を形成した。この保護層の厚さは１μ
ｍ、鉛筆硬度法による硬度は5Hであった。(Example 2) A solution obtained by completely dissolving 50 parts of polyvinyl formal in 100 parts of formic acid was applied on the surface of the charge transfer layer of the same photoreceptor for organic electrophotography as in Example 1, and then applied at a temperature of 80 ° C. Heating was performed for a time to form an insulating protective layer. The thickness of this protective layer is 1μ
m, the hardness by the pencil hardness method was 5H.
またこの本発明による感光体を帯電，露光，現像，転
写およびクリーニングからなる実施例１と同じ電子写真
装置を組込んで複写を行ったところ、本発明絶縁保護層
を設けていない感光体では、５万枚の複写で３μｍ電荷
移動層が摩耗したが、本発明感光体では10万枚複写して
も絶縁保護層の摩耗量は0.3μｍに過ぎなかった。When the same electrophotographic apparatus as in Example 1 comprising charging, exposure, development, transfer and cleaning was incorporated into the photoreceptor according to the present invention and copying was performed, the photoreceptor without the insulating protective layer according to the present invention showed: The charge transfer layer of 3 μm was abraded by copying 50,000 sheets, but the abrasion loss of the insulating protective layer was only 0.3 μm in the photoreceptor of the present invention even after copying 100,000 sheets.
（比較例１） 実施例１と同じ有機電子写真用感光体の電荷移動層面
上に、トリクレン300部中にポリビニルホルマール50部
を完全溶解させたものを塗布したのち、温度100℃で２
時間加熱して絶縁保護層を形成した。この絶縁保護層の
鉛筆硬度法による硬度は、前記本発明実施例１および２
における硬度と5Hより遥かに低い2Hであった。また実施
例１と同じ電子写真装置に組込んで複写を行ったとこ
ろ、本発明実施例における12万枚に比べて遥かに少ない
６万枚での複写で黒すじが発生した。(Comparative Example 1) A solution prepared by completely dissolving 50 parts of polyvinyl formal in 300 parts of trichlene was applied onto the surface of the charge transfer layer of the same photoreceptor for organic electrophotography as in Example 1, and then heated at 100 ° C.
Heating was performed for a time to form an insulating protective layer. The hardness of the insulating protective layer according to the pencil hardness method was determined according to Examples 1 and 2 of the invention.
Hardness and 2H which is much lower than 5H. Further, when copying was carried out by incorporating the same electrophotographic apparatus in Example 1, black streaks occurred in copying on 60,000 sheets, which is far less than 120,000 sheets in the embodiment of the present invention.
（比較例２） 実施例１と同じ有機電子写真用感光体の電荷移動層の
面上に、クロロホルム300部中に完全溶解かせたポリカ
ーボネート50部をスプレーにより塗布して、温度80℃で
２時間加熱して絶縁保護層を形成した。鉛筆硬度法によ
る硬度は3Hであった。また前記実施例１と同様の電子写
真装置に組込んで複写を行ったところ、本発明実施例の
12万枚に比べて遥かに少ない３万枚で黒すじが発生し
た。また保護層にセロハンテープを貼着したのち剥離し
てテープへの付着物を分析したところ、有機光導電材料
の混入が認められた。(Comparative Example 2) 50 parts of polycarbonate completely dissolved in 300 parts of chloroform was applied by spraying on the surface of the charge transfer layer of the same photoreceptor for organic electrophotography as in Example 1, and the temperature was 80 ° C for 2 hours. Heat was applied to form an insulating protective layer. The hardness by the pencil hardness method was 3H. Further, when copying was carried out by incorporating the same electrophotographic apparatus in the first embodiment,
Black streaks occurred on 30,000 sheets, which is far less than 120,000 sheets. When a cellophane tape was adhered to the protective layer and peeled off, and the attached matter on the tape was analyzed, it was found that an organic photoconductive material was mixed.
（発明の効果） 以上の説明から明らかなように本発明によれば、耐摩
耗性にすぐれた有機電子写真用感光体を提供できるもの
で、有機電子写真用感光体の長寿命化や画質の向上に大
きな効果を発揮する。(Effects of the Invention) As is apparent from the above description, according to the present invention, it is possible to provide an organic electrophotographic photosensitive member having excellent abrasion resistance. It has a great effect on improvement.
第１図は従来の有機電子写真用感光体の説明図、第２図
は本発明有機電子写真用感光体の説明図である。 （１）……導電性支持体、（２）……電荷発生層、
（３）……電荷移動層、（４）（５）……保護層。FIG. 1 is an explanatory view of a conventional photoreceptor for organic electrophotography, and FIG. 2 is an explanatory view of a photoreceptor for organic electrophotography of the present invention. (1) ... conductive support, (2) ... charge generation layer,
(3) ... charge transfer layer, (4) (5) ... protective layer.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉留 光広 山梨県甲府市宮原町1014番地 山梨電子 工業株式会社内 (56)参考文献 特開 昭47−15143（ＪＰ，Ａ) 特開 昭62−201460（ＪＰ，Ａ) 特開 昭62−159149（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Mitsuhiro Yoshidome 1014 Miyahara-cho, Kofu-shi, Yamanashi Yamanashi Electronics Industry Co., Ltd. (56) References JP-A-47-15143 (JP, A) JP-A-62-201460 (JP, A) JP-A-62-159149 (JP, A)
Claims (1)
層よりなる有機光導電層を設け、更にその上に絶縁保護
層を設けた有機電子写真用感光体において、 前記絶縁保護層が酢酸またはギ酸またはこれらの混合物
を溶媒とする、ポリビニルホルマールを用いて形成され
ていることを特徴とする有機電子写真用感光体。1. An organic electrophotographic photoreceptor comprising an organic photoconductive layer comprising a charge generation layer and a charge transfer layer provided on a surface of a conductive support, and further comprising an insulating protective layer provided thereon. A photoreceptor for organic electrophotography, wherein the photoreceptor is formed using polyvinyl formal using acetic acid, formic acid or a mixture thereof as a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33078190A JP2704670B2 (en) | 1990-11-30 | 1990-11-30 | Photoreceptor for organic electrophotography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33078190A JP2704670B2 (en) | 1990-11-30 | 1990-11-30 | Photoreceptor for organic electrophotography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04204540A JPH04204540A (en) | 1992-07-24 |
| JP2704670B2 true JP2704670B2 (en) | 1998-01-26 |
Family
ID=18236478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33078190A Expired - Fee Related JP2704670B2 (en) | 1990-11-30 | 1990-11-30 | Photoreceptor for organic electrophotography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2704670B2 (en) |
-
1990
- 1990-11-30 JP JP33078190A patent/JP2704670B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04204540A (en) | 1992-07-24 |
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